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Application of lithium complex in hydroboration reaction of nitrile

A complex and ligand technology, applied in catalytic reactions, lithium organic compounds, organic compounds/hydrides/coordination complex catalysts, etc. Simple structure, reduced catalyst dosage, and easy synthesis

Inactive Publication Date: 2020-10-09
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, compared with the research of β-diimine anionic ligands in organometallic chemistry, the application research of β-ketoimine anionic ligands is less
There is no report about the compounds (complexes) of dianion β-ketoimine ligands and their application in hydroboration

Method used

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  • Application of lithium complex in hydroboration reaction of nitrile
  • Application of lithium complex in hydroboration reaction of nitrile
  • Application of lithium complex in hydroboration reaction of nitrile

Examples

Experimental program
Comparison scheme
Effect test

Synthetic example

[0026] M-phenyl bridged β-ketimine ligand (L ph H 2 )Synthesis

[0027]

[0028] Add 150 ml of absolute ethanol, 10.8 g of m-phenylenediamine (100 mmol), 20.5 mL of acetylacetone (200 mmol), and catalytic amount of p-toluenesulfonic acid into a three-necked flask. Heat to reflux for 24 hours to obtain a reddish brown liquid and light The yellow solid mixture was filtered with suction, and the solid was recrystallized with absolute ethanol to obtain 24.5 g of light yellow needle crystals, with a yield of 90%, which was ligand L ph H 2 . 1 H NMR(400 MHz, CDCl 3 ): δ 12.47 (2H, s, NH), 7.32-7.27 (1H, m, ArH), 6.94-6.91 (2H, m,ArH), 6.86 (1H, s, ArH), 5.21 (2H, s, CH=C( CH 3 )N), 2.10 (6H, s, CH 3 ), 2.01 (6H,s, CH 3 ). 13 C NMR (101 MHz, CDCl 3 ): δ 196.54 (COCH 3 ), 159.62 (C=CH), 139.63 (Ar-C), 129.71 (Ar-C), 121.45 (Ar-C), 120.43 (Ar-C), 98.20 (=CH), 29.25 (CH 3 ),19.94 (CH 3 ). HRMS (ESI-MS) calcd. for C 16 H 20 N 2 O 2 [M+H] + : 273.1558, found: 273.1633.

[0029] Deprotona...

Embodiment 1

[0035] Example one: [L ph’ Li 4 (THF) 4 ] 2 Catalytic reduction of benzonitrile and pinacol borane

[0036] Under an inert gas atmosphere, add 5.84 mg (0.005 mmol) of catalyst to the reaction flask after dehydration and deoxygenation, and add benzonitrile (64.4 μL, 0.5 mmol) and pinacol borane (159.6 μL) with a pipette. ,1.1 mmol), THF (200 μL), in 60 o After reacting with C for 120 min, use mesitylene (69.6 μL, 0.5 mmol) as the internal standard, stir evenly, pipette a drop into the NMR tube, add CDCl 3 Make a solution. Calculated 1 The H spectrum yield is 96%. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ) δ 7.31-7.14 (m, 5H, ArCH), 4.23 (s,2H, NCH 2 ), 1.18 (s, 24H, OBpin).

Embodiment 2

[0041] Embodiment two: [L ph’ Li 4 (THF) 4 ] 2 Catalytic reduction of benzonitrile and pinacol borane

[0042] Under an inert atmosphere, add 5.84 mg of catalyst to the reaction flask after dehydration and deoxygenation, and add benzonitrile (64.4 μL, 0.5 mmol) and pinacol borane (159.6 μL, 1.1 mmol) with a pipette. , THF (200 μL), react at room temperature (25℃) for 24 h, use mesitylene (69.6 μL, 0.5 mmol) as the internal standard, stir evenly, pipette a drop into the NMR tube, add CDCl 3 Make a solution. Calculated 1 The H-spectrum yield was 76%.

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Abstract

The invention relates to a lithium compound and application thereof in the field of organic synthesis, in particular to application of a lithium complex in a hydroboration reaction of nitrile. Compared with the research of the beta-diimine anion ligand on organometallic chemistry, the application research of the beta-ketimine anion ligand is less, and the compound (complex) of the double-anion beta-ketimine ligand and the application thereof and the hydroboration reaction are not reported so far. The compound is applied to the hydroboration reaction of nitrile, and efficient reduction of nitrile and pinacol borane can be achieved.

Description

Technical field [0001] The invention relates to a lithium compound and its application in the field of organic synthesis, in particular to a deprotonated β-ketoimide lithium compound, a preparation method thereof and its application in the borohydride reaction of nitrile. Background technique [0002] The borohydride reaction is widely used in the production of modern metal chemistry and agrochemicals. Organoboron compounds serve as versatile precursors in carbon-carbon and carbon-heteroatom bond formation reactions, such as Suzuki-Miyaura reaction and Chan-Lam cross coupling. The hydroboration of various unsaturated bonds has been widely explored, and the hydroboration of nitriles has received more and more attention in recent years. Among the unsaturated functional groups, the C≡N bond in organic nitrile is considered to be very stable due to its higher bond dissociation energy (179.3 kcal / mol, 750.0kJ / mol). Therefore, the inertness of the C≡N bond makes it difficult for nitr...

Claims

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Application Information

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IPC IPC(8): B01J31/22C07F1/02C07F5/02
CPCB01J31/2217B01J2231/341B01J2531/0238B01J2531/11C07F1/005C07F5/022
Inventor 薛明强康子晗徐晓娟周帅武振杰颜丹丹
Owner SUZHOU UNIV
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